NOx and particulate matter (soot) emissions from diesel engines are an environmental problem. Several countries, including the United States, have long had regulations pending that will limit NOx, and particulate matter (soot) emissions from trucks and other diesel-powered vehicles. Manufacturers and researchers have put considerable effort toward meeting those regulations. Diesel particulate filters (DPFs) have been proposed for controlling particulate matter emissions. A number of different solutions have been proposed for controlling NOx emissions.
In gasoline powered vehicles that use stoichiometric fuel-air mixtures, NOx emissions can be controlled using three-way catalysts. In diesel-powered vehicles, which use compression ignition, the exhaust is generally too oxygen-rich for three-way catalysts to be effective.
One set of approaches for controlling NOx emissions from diesel-powered vehicles involves limiting the creation of pollutants. Techniques such as exhaust gas recirculation and partially homogenizing fuel-air mixtures are helpful in reducing NOx emissions, but these techniques alone are not sufficient. Another set of approaches involves removing NOx from the vehicle exhaust. These approaches include the use of lean-burn NOx catalysts, selective catalytic reduction (SCR), and lean NOx traps (LNTs).
Lean-burn NOx catalysts promote the reduction of NOx under oxygen-rich conditions. Reduction of NOx in an oxidizing atmosphere is difficult. It has proven challenging to find a lean-burn NOx catalyst that has the required activity, durability, and operating temperature range. Lean-burn NOx catalysts also tend to be hydrothermally unstable. A noticeable loss of activity occurs after relatively little use. Lean-burn NOx catalysts typically employ a zeolite wash coat, which is thought to provide a reducing microenvironment. The introduction of a reductant, such as diesel fuel, into the exhaust is generally required and introduces a fuel economy penalty of 3% or more. Currently, peak NOx conversion efficiencies for lean-burn NOx catalysts are unacceptably low.
SCR generally refers to selective catalytic reduction of NOx by ammonia. The reaction takes place even in an oxidizing environment. The NOx can be temporarily stored in an adsorbent or ammonia can be fed continuously into the exhaust. SCR can achieve high levels of NOx reduction, but there is a disadvantage in the lack of infrastructure for distributing ammonia or a suitable precursor. Another concern relates to the possible release of ammonia into the environment.
To clarify the state of a sometime ambiguous nomenclature, it should be noted that in the exhaust aftertreatment art, the terms “SCR catalyst” and “lean NOx catalyst” are occasionally used interchangeably. Where the term “SCR” is used to refer just to ammonia-SCR, as it often is, SCR is a special case of lean NOx catalysis. Commonly when both types of catalysts are discussed in one reference, SCR is used with reference to ammonia-SCR and lean NOx catalysis is used with reference to SCR with reductants other than ammonia, such as SCR with hydrocarbons.
LNTs are devices that adsorb NOx under lean exhaust conditions and reduce and release the adsorbed NOx under rich exhaust conditions. A LNT generally includes a NOx adsorbent and a catalyst. The adsorbent is typically an alkaline earth compound, such as BaCO3 and the catalyst is typically a combination of precious metals, such as Pt and Rh. In lean exhaust, the catalyst speeds oxidizing reactions that lead to NOx adsorption. In a reducing environment, the catalyst activates reactions by which adsorbed NOx is reduced and desorbed. In a typical operating protocol, a reducing environment will be created within the exhaust from time-to-time to remove accumulated NOx and thereby regenerate (denitrate) the LNT.
Creating a reducing environment for LNT regeneration involves eliminating most of the oxygen from the exhaust and providing a reducing agent. Except where the engine can be run stoichiometric or rich, a portion of the reductant reacts within the exhaust to consume oxygen. The amount of oxygen to be removed by reaction with reductant can be reduced in various ways. If the engine is equipped with an intake air throttle, the throttle can be used. However, at least in the case of a diesel engine, it is generally necessary to eliminate some of the oxygen in the exhaust by combustion or reforming reactions with reductant that is injected into the exhaust.
The reactions between reductant and oxygen can take place in the LNT, but it is generally preferred for the reactions to occur in a catalyst upstream of the LNT, whereby the heat of reaction does not cause large temperature increases within the LNT at every regeneration.
Reductant can be injected into the exhaust by the engine fuel injectors or separate injection devices. For example, the engine can inject extra fuel into the exhaust within one or more cylinders prior to expelling the exhaust. Alternatively, or in addition, reductant can be injected into the exhaust downstream of the engine.
U.S. Pat. Pub. No. 2004/0050037 (hereinafter “the '037 publication”) describes an exhaust treatment system with a fuel reformer placed in the exhaust line upstream of a LNT. The reformer includes both oxidation and reforming catalysts. The reformer both removes excess oxygen and converts the diesel fuel reductant into more reactive reformate.
The operation of an inline reformer can be modeled in terms of the following three reactions:0.684 CH1.85+O2→0.684 CO2+0.632 H2O  (1)0.316 CH1.85+0.316 H2O→0.316 CO+0.608 H2  (2)0.316 CO+0.316 H2O→0.316 CO2+0.316 H2  (3)wherein CH1.85 represents an exemplary reductant, such as diesel fuel, with a 1.85 ratio between carbon and hydrogen. Reaction (1) is exothermic complete combustion by which oxygen is consumed. Reaction (2) is endothermic steam reforming. Reaction (3) is the water gas shift reaction, which is comparatively thermal neutral and is not of great importance in the present disclosure, as both CO and H2 are effective for regeneration.
The inline reformer of the '037 publication is designed to be rapidly heated and to then catalyze steam reforming. Temperatures from about 500 to about 700° C. are said to be required for effective reformate production by this reformer. These temperatures are substantially higher than typical diesel exhaust temperatures. The reformer is heated by injecting fuel at a rate that leaves the exhaust lean, whereby Reaction (1) takes place. After warm up, the fuel injection rate is increased to provide a rich exhaust. Depending on such factors as the exhaust oxygen concentration, the fuel injection rate, and the exhaust temperature, the reformer tends to either heat or cool as reformate is produced. Reformate is an effective reductant for LNT denitration.
U.S. Pat. No. 6,006,515 suggests that a LNT may be regenerated more efficiently by either longer chain or shorter chain hydrocarbons, depending on the LNT composition and the temperature at which regeneration takes place. In order to be able to control the selection between long and short chain hydrocarbons, the patent proposes two fuel injectors, one in the exhaust manifold upstream of the turbocharger and one in the exhaust line immediately before the LNT. Due to the high temperatures in the exhaust upstream of the turbocharger, fuel injected with the manifold fuel injector is said to undergo substantial cracking to form shorter chain hydrocarbons.
During denitrations, much of the adsorbed NOx is reduced to N2, although a portion of the adsorbed NOx is released without having been reduced and another portion of the adsorbed NOx is deeply reduced to ammonia. The NOx release occurs primarily at the beginning of the regeneration. The ammonia production has generally been observed towards the end of the regeneration.
U.S. Pat. No. 6,732,507 proposes a system in which a SCR catalyst is configured downstream of the LNT in order to utilize the ammonia released during denitration. The LNT is provided with more reductant over the course of a regeneration than required to remove the accumulated NOx in order to facilitate ammonia production. The ammonia is utilized to reduce NOx slipping past the LNT and thereby improves conversion efficiency over a stand-alone LNT.
U.S. Pat. Pub. No. 2004/0076565 (hereinafter “the '565 publication”) also describes hybrid systems combining LNT and SCR catalysts. In order to increase ammonia production, it is proposed to reduce the rhodium loading of the LNT. In order to reduce the NOx release at the beginning of the regeneration, it is proposed to eliminate oxygen storage capacity from the LNT.
In addition to accumulating NOx, LNTs accumulate SOx. SOx is the combustion product of sulfur present in ordinarily fuel. Even with reduced sulfur fuels, the amount of SOx produced by combustion is significant. SOx adsorbs more strongly than NOx and necessitates a more stringent, though less frequent, regeneration. Desulfation requires elevated temperatures as well as a reducing atmosphere. The temperature of the exhaust can be elevated by engine measures, particularly in the case of a lean-burn gasoline engine, however, at least in the case of a diesel engine, it is often necessary to provide additional heat. Typically, this heat can be provided through the same types of reactions as used to remove excess oxygen from the exhaust. Once the LNT is sufficiently heated, the exhaust is made rich by measures like those used for LNT denitration.
Diesel particulate filters must also be regenerated. Regeneration of a DPF is to remove accumulated soot. Two general approaches are continuous and intermittent regeneration. In continuous regeneration, a catalyst is provided upstream of the DPF to convert NO to NO2. NO2 can oxidize soot at typical diesel exhaust temperatures and thereby effectuate continuous regeneration. A disadvantage of this approach is that it requires a large amount of expensive catalyst.
Intermittent regeneration involves heating the DPF to a temperature at which soot combustion is self-sustaining in a lean environment. Typically this is a temperature from about 400 to about 600° C., depending in part on what type of catalyst coating has been applied to the DPF to lower the soot ignition temperature. A challenge in using this approach is that soot combustion tends to be non-uniform and high local temperatures can lead to degradation of the DPF.
Because both DPF regeneration and LNT desulfation require heating, it has been proposed to carry out the two operation successively. The main barrier to combining desulfation and DPF regeneration has been that desulfation requires rich condition and DPF regeneration requires lean conditions. U.S. Pat. Pub. No. 2001/0052232 suggests heating the DPF to initiate soot combustion, and afterwards desulfating the LNT, whereby the LNT does not need to be separately heated. Similarly, U.S. Pat. Pub. No. 2004/0113249 describes adding reductant to the exhaust gases to heat the DPF, ceasing the addition of reductant to allow the DPF to regenerate, and then resuming reductant addition to desulfate the LNT.
U.S. Pat. Pub. No. 2004/0116276 suggests close coupling a DPF and a LNT, with the DPF upstream of the LNT. The publication suggests that this close-coupling allows CO produced in the DPF during DPF regeneration to assist regeneration of the downstream LNT by removing NOx during DPF regeneration in a lean environment.
In spite of advances, there continues to be a long felt need for an affordable and reliable exhaust treatment system that is durable, has a manageable operating cost (including fuel penalty), and is practical for reducing NOx emissions from diesel engines to a satisfactory extent in the sense of meeting U.S. Environmental Protection Agency (EPA) regulations effective in 2010 and other such regulations.